This invention relate""s to certain carboxanilides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in agronomic and nonagronomic environments 
wherein:
A is H;
E is H or C1-C3 alkyl; or
A and E can be taken together to form xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94S(O)xe2x80x94, xe2x80x94S(O)2xe2x80x94, xe2x80x94NR8xe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94N(R8)CH2xe2x80x94, substituted xe2x80x94CH2xe2x80x94 and substituted xe2x80x94CH2CH2xe2x80x94, the substituents on each carbon independently selected from 1-2 halogen and 1-2 methyl;
G is selected from the group consisting of 
W is N or CR4;
X is CR5R6, O, S, NR7 or a direct bond, provided that when W is N, then X is other than a direct bond;
Y is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C3 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylalkyl, NR9R10, Nxe2x95x90CR11R12, OR7, COR13, CO2R14 or C1-C6 alkyl substituted by at least one group selected from halogen, C1-C3 alkoxy, CN, NO2, S(O)rR15, COR13, CO2R14 and optionally substituted phenyl;
Z is O or S;
each R1 and R2 is independently selected from the group consisting of C1-C6 haloalkyl, C2-C6 haloalkenyl, halogen, CN, NO2, OR16, S(O)rR15, OS(O)2R15, CO2R14, C(O)R13, C(O)NR9R10, SO2NR9R10, SF5, optionally substituted phenyl and optionally substituted benzyl; or when m or n is 2, (R1)2 can be taken together or (R2)2 can be taken together as xe2x80x94OCH2Oxe2x80x94, xe2x80x94OCF2Oxe2x80x94, xe2x80x94OCH2CH2Oxe2x80x94, xe2x80x94CH2C(CH3)2Oxe2x80x94, xe2x80x94CF2CF2O or xe2x80x94OCF2CF2Oxe2x80x94;
R3 is selected from the group consisting of J, C(R17)xe2x95x90Nxe2x80x94Oxe2x80x94R18, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 alkoxylalkyl, C3-C8 alkoxycarbonylalkyl, CO2R14, C(O)R13, C(O)NR9R10, C(S)NR9R10, C(S)R13, C(S)SR13, CN, and optionally substituted phenyl; or R3 is C2-C6 epoxyalkyl optionally substituted with a group selected from C1-C3 alkyl, CN, C(O)R13, CO2R14 and optionally substituted phenyl; or R3 is C1-C6 alkyl substituted with a group selected from C(O)NR9R10, COR13, CO2R14, S(O)mR15, SCN, CN, C1-C2 haloalkoxy, SiR19R20R21, NR9R10, NO2, OC(O)R13, xe2x80x94P(O)(OR22)2, optionally substituted phenyl, and J;
J is a nonaromatic or aromatic 5- or 6-membered heterocyclic ring, bonded through carbon or nitrogen, containing 1-4 heteroatoms independently selected from the group consisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, optionally containing one carbonyl moiety and optionally substituted;
R4, R5 and R6 are each independently H or C1-C4 alkyl;
each R7 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, SO2NR9R10, SO2R13, COR9, CONR9R10, CO2R13, optionally substituted phenyl or optionally substituted benzyl;
each R8 is independently H, C1-C4 alkyl, C1-C4 alkoxyalkyl, CO2R13, SO2R13, or optionally substituted benzyl;
each R9 and each R11 is independently H, C1-C4 alkyl, C1-C4 haloalkyl or optionally substituted phenyl;
each R10 and each R12 is independently H or C1-C4 alkyl; or
each pair of R9 and R10 when attached to the same atom or each pair of R11 and R12 when attached to the same atom independently can be taken together as xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2CH2CH2xe2x80x94 or xe2x80x94CH2CH2OCH2CH2xe2x80x94, each of which is optionally and independently substituted with 1 or 2 CH3 groups;
each R13 and each R15 is independently H, C1-C4 alkyl, C1-C4 haloalkyl or optionally substituted phenyl;
each R14 is independently H, C1-C4 alkyl, C1-C4 haloalkyl or optionally substituted benzyl;
R16 is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, optionally substituted phenyl and optionally substituted benzyl;
R17 is selected from the group consisting of H, Cl, C1-C4 alkyl, C1-C4 alkoxy, C1-C2 thioalkyl and CN;
R18 is selected from the group consisting of H, C1-C4 alkyl, C2-C3 alkylcarbonyl and C2-C3 alkoxycarbonyl;
R19 and R20 are each independently C1-C3 alkyl;
R21 is selected from the group consisting of H, C1-C3 alkyl and optionally substituted phenyl;
each R22 is independently H or C1-C4 alkyl;
each m and n are independently 1 to 3; and
r is 0, 1 or 2.
In the above recitations, the term xe2x80x9calkylxe2x80x9d, used either alone or in compound words such as xe2x80x9calkylthioxe2x80x9d or xe2x80x9chaloalkylxe2x80x9d includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. The term xe2x80x9c1-2 alkylxe2x80x9d indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. xe2x80x9cAlkenylxe2x80x9d includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. xe2x80x9cAlkenylxe2x80x9d also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. xe2x80x9cAlkynylxe2x80x9d includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. xe2x80x9cAlkynylxe2x80x9d can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. xe2x80x9cAlkoxyxe2x80x9d includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. xe2x80x9cAlkoxyalkylxe2x80x9d denotes alkoxy substitution on alkyl. Examples of xe2x80x9calkoxyalkylxe2x80x9d include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. xe2x80x9cAlkylthioxe2x80x9d includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. xe2x80x9cAlkylthioalkylxe2x80x9d denotes alkylthio substitution on alkyl. Examples of xe2x80x9calkylthioalkylxe2x80x9d include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. xe2x80x9cAlkylsulfinylxe2x80x9d includes both enantiomers of an alkylsulfinyl group. Examples of xe2x80x9calkylsulfinylxe2x80x9d include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of xe2x80x9calkylsulfonylxe2x80x9d include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(O)2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfinyl isomers. xe2x80x9cCyanoalkylxe2x80x9d denotes an alkyl group substituted with one cyano group. Examples of xe2x80x9ccyanoalkylxe2x80x9d include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. xe2x80x9cCycloalkylxe2x80x9d includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples ofxe2x80x9ccycloalkylalkylxe2x80x9d include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. Examples of xe2x80x9ccycloalkylalkoxyxe2x80x9d include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups. Examples of xe2x80x9calkylcarbonylxe2x80x9d include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of xe2x80x9callcoxycarbonylxe2x80x9d include CH3OC(xe2x95x90O), CH3CH2OC(xe2x95x90O), CH3CH2CH2OC(xe2x95x90O), (CH3)2CHOC(xe2x95x90O) and different butoxy- or pentoxycarbonyl isomers. Examples of xe2x80x9calkoxycarbonylalkylxe2x80x9d include CH3OC(xe2x95x90O)CH2, CH3CH2OC(xe2x95x90O)CH2, CH3OC(xe2x95x90O)CH2CH2, CH3CHOC(xe2x95x90O)CH2CH2 and the different propoxy-, butoxy- or pentoxycarbonyl isomers.
The term xe2x80x9chalogenxe2x80x9d, either alone or in compound words such as xe2x80x9chaloalkylxe2x80x9d, includes fluorine, chlorine, bromine or iodine. The term xe2x80x9c1-2 halogenxe2x80x9d indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as xe2x80x9chaloalkylxe2x80x9d, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of xe2x80x9chaloalkylxe2x80x9d include F3C, ClCH2, CF3CH2 and CF3CCl2. The terms xe2x80x9chaloalkenylxe2x80x9d, xe2x80x9chaloalkynylxe2x80x9d, xe2x80x9chaloalkoxyxe2x80x9d, and the like, are defined analogously to the term xe2x80x9chaloalkylxe2x80x9d. Examples of xe2x80x9chaloalkenylxe2x80x9d include (Cl)2Cxe2x95x90CHCH2 and CF3CH2CHxe2x95x90CHCH2. Examples of xe2x80x9chaloalkynylxe2x80x9d include HCxe2x89xa1CCHCl, CF3Cxe2x89xa1C, CCl3Cxe2x89xa1C and FCH2Cxe2x89xa1CCH2. Examples of xe2x80x9chaloalkoxyxe2x80x9d include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O.
The term xe2x80x9caromatic ringxe2x80x9d denotes fully unsaturated carbocycles and heterocycles in which the ring is aromatic (where aromatic indicates that the Hxc3xcckel rule is satisfied for the ring system). The term xe2x80x9caromatic heterocyclic ringxe2x80x9d includes fully aromatic heterocycles (where aromatic indicates that the Hxc3xcckel rule is satisfied). The term xe2x80x9cnonaromatic heterocyclic ringxe2x80x9d denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hxc3xcckel rule is not satisfied. The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. The term xe2x80x9cbenzylxe2x80x9d denotes a xe2x80x94CH2C6H5 moiety in which the C6H5 ring is aromatic.
One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
The total number of carbon atoms in a substituent group is indicated by the xe2x80x9cCi-Cjxe2x80x9d prefix where i and j are numbers from 1 to 6. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i-j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R4 or R7, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
In Formula I, the term xe2x80x9coptionally substitutedxe2x80x9d in reference to certain phenyl, benzyl or J rings (see the definitions of Y, J, R1, R2, R3, R7, R8, R9, R11, R13, R14, R15, R16 and R21) refers to a phenyl, benzyl or J ring that is unsubstituted, or is substituted with at least one non-hydrogen group that does not extinguish the arthropodicidal activity possessed by the analog in which the phenyl, benzyl or J ring is unsubstituted. In the case of a phenyl ring or a benzyl ring, the optional non-hydrogen group is attached to a carbon atom contained within the aromatic ring. In the case of J, a nonaromatic or aromatic 5- or 6-membered heterocyclic ring, bonded through carbon or nitrogen, containing 1-4 heteroatoms independently selected from the group consisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, optionally containing one carbonyl moiety and optionally substituted, the optional non-hydrogen group is attached to either a carbon atom or a nitrogen within the ring. Examples of optionally substituted phenyl, benzyl or J rings are those wherein said rings are optionally substituted with R23 and optionally substituted with R24, wherein
each R23 is independently selected from the group consisting of 1-2 halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfonyl and C1-C2 haloalkylsulfonyl; and
each R24 is independently selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl and C1-C4 haloalkoxy.
Examples of phenyl, benzyl or J rings wherein said rings are optionally substituted with R23 and/or R24 include the rings illustrated in Exhibit 1 as a phenyl ring optionally substituted with R23 and/or R24, a benzyl ring optionally substituted with R23 and/or R24, 5- or 6-membered aromatic heterocyclic rings (J-1 to J-28), and 5- or 6-membered nonaromatic heterocyclic rings optionally containing one carbonyl moiety (J-29 to J-50). As with the carbon atoms in the ring, the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R23 and/or R24. Although the R23 and/or R24 groups are shown in the structures illustrated in Exhibit 1, it is noted that R23 and/or R24 do not need to be present since they are optional substituents.

Preferred compounds for reasons of better activity and/or ease of synthesis are:
Preferred 1. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein:
Y is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C3 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylalkyl, NR9R10, Nxe2x89xa1CR11R12, OR7, COR13, CO2R14 or C1-C6 alkyl substituted by at least one group selected from halogen, C1-C3 alkoxy, CN, NO2, S(O)rR15, COR13, CO2R14 and phenyl optionally substituted with R23 and R24;
each R1 and R2 is independently selected from the group consisting of C1-C6 haloalkyl, C2-C6 haloalkenyl, halogen, CN, NO2, OR16, S(O)rR15, OS(O)2R15, CO2R14, C(O)R13, C(O)NR9R10, SO2NR9R10, SF5, phenyl optionally substituted with R23 and R24 and benzyl optionally substituted with R23 and R24; or when m or n is 2, (R1)2 can be taken together or (R2)2 can be talen together as xe2x80x94OCH2Oxe2x80x94, xe2x80x94OCF2Oxe2x80x94, xe2x80x94OCH2CH2Oxe2x80x94, xe2x80x94CH2C(CH3)2Oxe2x80x94, xe2x80x94CF2CF2O or xe2x80x94OCF2CF2Oxe2x80x94;
R3 is selected from the group consisting of J, C(R17)xe2x95x90Nxe2x80x94Oxe2x80x94R18, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 alkoxylalkyl, C3-C8 alkoxycarbonylalkyl, CO2R14, C(O)R13, C(O)NR9R10, C(S)NR9R10, C(S)R13, C(S)SR13, CN, and phenyl optionally substituted with R23 and R24; or R3 is C2-C6 epoxyalkyl optionally substituted with a group selected from C1-C3 alkyl, CN, C(O)R13, CO2R14 and phenyl optionally substituted with R23 and R24; or R3 is C1-C6 alkyl substituted with a group selected from C(O)NR9R10, COR13, CO2R14, S(O)mR15, SCN, CN, C1-C2 haloalkoxy, SiR19R20R21, NR9R10, NO2, OC(O)R13, xe2x80x94P(O)(OR22)2, phenyl optionally substituted with R23 and R24, and J;
J is a nonaromatic or aromatic 5- or 6-membered heterocyclic ring, bonded through carbon or nitrogen, containing 1-4 heteroatoms independently selected from the group consisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, optionally containing one carbonyl moiety and optionally substituted with R23 and R24;
each R7 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, SO2NR9R10, SO2R13, COR9, CONR9R10, CO2R13, phenyl optionally substituted with R23 and R24 or benzyl optionally substituted with R23 and R24;
each R8 is independently H, C1-C4 alkyl, C1-C4 alkoxyalkyl, CO2R13, SO2R13, or benzyl optionally substituted with R23 and R24;
each R9 and each R11 is independently H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl optionally substituted with R23 and R24;
each R10 and each R12 is independently H or C1-C4 alkyl; or
each pair of R9 and R10 when attached to the same atom or each pair of R11 and R12 when attached to the same atom independently can be taken together as xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2CH2CH2xe2x80x94 or xe2x80x94CH2CH2OCH2CH2xe2x80x94, each of which is optionally and independently substituted with 1 or 2 CH3 groups;
each R13 and each R15 is independently H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl optionally substituted with R23 and R24;
each R14 is independently H, C1-C4 alkyl, C1-C4 haloalkyl or benzyl optionally substituted with R23 and R24;
R16 is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, phenyl optionally substituted with R23 and R24 and benzyl optionally substituted with R23 and R24;
R21 is selected from the group consisting of H, C1-C3 alkyl and phenyl optionally substituted with R23 and R24;
each R23 is independently selected from the group consisting of 1-2 halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfonyl and C1-C2 haloalkylsulfonyl; and
each R24 is independently selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl and C1-C4 haloalkoxy.
Most preferred is the compound of Preferred 1:
7-Chloro-9,9xcex1-dihydro-9xcex1-propyl-N-[4-(trifluoromethoxy)phenyl]-1H-indeno[1,2-e]-1,2,4-triazine-3-Carboxamide.
This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of the invention and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. The preferred compositions of the present invention are those which comprise the above preferred compounds.
This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds.
The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-12. The definitions of A, E, G, W, X, Y, R2, R3, Z, R4, R5, R6 and R7 in the compounds of Formulae II-XVI below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Ic are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ic are as defined above for Formula I. In the Schemes, Rk is equivalent to Rk where k is a number from 1 to 7.
Transformations similar to those described in the Schemes have been reported in the references associated with the Schemes. The reactions may be run at temperatures from xe2x88x92100 to 150xc2x0 C. with temperatures from 0 to 120xc2x0 C. being preferred. Many solvents are acceptable including ethereal solvents such as diethyl ether, THF, dioxane, or glyme, halocarbon or hydrocarbon solvents such as chlorobenzene, CH2Cl2, hexanes, benzene, toluene or xylene, ketones such as acetone, and polar aprotic solvents such as acetonitrile, dimethylformamide, dimethylacetamide, and dimethylsulfoxide. In some instances aqueous solvents or lower alcohols may be used. One skilled in the art will recognize that the transformations may also be carried out using combinatorial chemistry techniques. 
Compounds of Formula Ia (see Scheme 1 on previous page) can be prepared by reacting a compound of Formula II with a compound of Formula III using procedures known to one skilled in the art (for Q is Cl, see March, Advanced Organic Chemistry, 3rd Edition, 1985, p. 370-376; for Q is OR, e.g., J. Chem. Soc., 1954, 1188; Synth. Commun., 1982, 12, 989; Tetrahedron Lett., 1971, 321).
Alternatively, compounds of Formula Ib can be prepared by condensing a compound of Formula IV with a compound of Formula V in the presence of a base. 
Compounds of Formula IIa can be prepared by reacting a compound of Formula VI with compound of Formula VII using procedures known to one skilled in the art (e.g. Angew. Chem. int. Ed. Engl., 1981, 20, 296). 
Compounds of Formula IIb (Q is OR) can be prepared by reacting a compound of Formula IV with a compound of Formula VIII using procedures analogous to those described for Scheme 2. One skilled in the art will recognize that compounds of Formula IIb (Q is OR) can be converted into compounds of Formula II wherein Q is Cl using known procedures (e.g. U.S. Pat. No. 5,708,170; March, Advanced Organic Chemistry, 3rd Edition, pp. 334-338, 388). 
Compounds of Formula X and IVa can be prepared from compounds of Formula IX using procedures that are known to one skilled in the art (e.g., J. Org. Chem., 1988, 53, 2131; Tetrahedron Lett., 1991, 32, 5927; J. Am. Chem. Soc., 1986, 108, 6395). 
Compounds of Formula IVb (X is O) can be prepared from compounds of Formula XI using procedures that are known to one skilled in the art (e.g., Chem. Pharm. Bull., 1992, 40, 683). Compounds of Formula XI can be prepared from compounds of Formula IX using procedures that are known to one skilled in the art (for LG is Cl, Br, I, e.g., J. Am. Chem. Soc., 1959, 81, 1201; J. Org. Chem., 1968, 33, 419.1; and for LG is OMs (OSO2CH3), OTf, (OSO2CF3) and OTs (OSO2C6H4CH3), e.g., J. Org. Chem., 1985, 50, 5148; Tetrahedron Lett., 1992, 33, 7647; J. Org. Chem., 1982, 47, 2487). 
Compounds of Formula IVc (X is S) can be prepared by animation of compounds of Formula XII (X is S) using procedures that are known to one skilled in the art (e.g., J. Org. Chem., 1972, 37, 3820; Synthesis, 1991, 327; Synthetic Commun., 1986, 16, 899). 
Compounds of Formula IVd (X is CR5R6) can be prepared from compounds of Formula IX using procedures that are known to one skilled in the art (e.g., J. Am. Chem. Soc., 1942, 64, 45; Chem. Pharm. Bull., 1984, 32, 4323). 
Compounds of Formula VI can be prepared by condensation of compounds of Formulae XIIa and XIII using procedures that are known to one skilled in the art (e.g. March, Advanced Organic Chemistry, 3rd Edition, pp. 796-798). 
Compounds of Formula XV can be prepared from compounds of Formula XIV using procedures that are known to one skilled in the art (e.g., J. Chem. Soc. Chem. Commun., 1974, 826; Justus Liebigs Ann. Chem.,1949, 562). Compounds of Formula V can be prepared using procedures described for the reaction in Scheme 10. 
Compounds of Formula VII can be prepared from compounds of Formula XVI using procedures that are known to one skilled in the art (e.g., J. Org Chem., 1973, 38, 1437; J. Heterocyclic Chem., 1988, 25, 651). 
Compounds of Formula Ic, compounds of Formula I wherein Z is S, can be prepared by treating compounds of Formula Ia (I wherein Z is O) with thionating reagents such as P2S5 or Lawesson""s reagent [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide] as illustrated in Scheme 12 (see Bull. Soc. Chim. Belg., 1978, 87, 229; and Tetrahedron Lett., 1983, 24, 3815). 
Compounds of Formulae IX and XII can be prepared using procedures described in U.S. Pat. No. 5,708,170.
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1H NMR spectra are reported in ppm downfield from tetramethylsilane; 19F NMR spectra are reported in ppm relative to CFCl3; s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, dd is doublet of doublets, dt is doublet of triplets, and br s is broad singlet.